Heat and sulphur resistant tire curing bag



15, 1942. P. K. FROLICH r:rm. 2,305,412

Patented. Dec. 15,4942

s PATENT OFFICE HEAT:AND SULPHUR RESIST ANT TIRE CUBING BAG Per K. Frolich, Westfleld, N. J. und Bands D. Hineline, Mount Vernon, N. Y., assignors, by mesne assigmnents, toJasco,-Incorpotated, a corporatlon o! Louislana.

Applicatioh November 24, 1939, Serial N0. 305,822

8 Claims.

This invention relates to the manufacture of tlres, and relates particularly to a. new und useful tlle a1r bag for the vulcanlzing of rubber tlres in the mold.

In the manufacture of rubber tire, casings lt 1s customary 1:0 compound the crude gum rubber wlth a wlde variety of substances, lncluding among others carbon b1ack, zinc oxlde, stearlc acid, mineral rubber, sulphur and accelerator substances. The cotton fabric which :ls to form the foundation for th a tire casing, that 1s, the carcass, is prepared by treatlng the cotton fabric with suitably compounded rubber to fi11 the interstices between the fibres, er 120 lmpregnate the fabric with a. suitable rubber compound or m1x. The fabric is then formed in layers to the desired contours o'f the tire, and a layer of compounded tread stock rubber is applied to the unter surface to' prepare the'casing for vul canizing. The vulcanizing is conducted in a steel mold, the inner surface 015 which has the desired tread contours in intaglio, or in reverse of the desired tread configuration. In order 110 !orce the tread fully lnto the interstices of the mold, it; is customary to use a rubber air ba.g, which is lnserted within the caslng, the casing und air bag inserted' int;o the mold, the mold closed, the air bag inflated wlth air 1:0 a substantia1 pressure, and the mold and conta.ined unvulcanized tire carcass and tread are then heated elther with live steam, or by electrlc heat 1:0 the desired vulcanizing temperature, which usually is in the neighborhood cf 140 C. to 145 C. for the appropriate tlme to cause -the desired vulcanizatlon.

Great difliculty is encountered, however, wlth such air bags.. The extent of vulcanization in a. given rubber compound is a. function of the amount of sulphur present, and if the amount of sulphur in the rubber exceeds about 5%, the rubber tends to lose lts elasticity and if the sulphur content exceeds about 25%, it loses 1ts elasticity entirely and becomes stifi, hard, a.nd brittle. In the curing of rubber tires, the sulphur in the tire casing mlgrates into the a.ir bag, and accordingly if the air bag 1s made of rubber, as has previously been necessary, the migrating sulphur, even in small amounts ca.uses the rubber to over-vulcanize rapidly to the point where wlthin a. comparatively short.time the rubber in the a.ir bag ls over-cured and in time is converted into so-called hard rubber, and the elasticity ls ent1rely lost.. When thls stage is reached, the a1r bag is no longer capable of forclng the tread stock on the carcass lnto the contours of the mold, and,-in consequence, defective tire casings are produced. since the desired design is not im1aressed upon the tread surface and the carcass dqes not; atta.in the proper size and Contours. Also, when -t his stage 13 reached, especially if attempts are madeto use a hardened air bag, grat difi'iculty 1s encoun tered in inserting lt within the carcas s, and in removing it from the carcass bothbg9 apse 01 the si:ifiness of theainbag, anglbtlse ofiihe tendency to break or tear during the operation. Thus, prolonged heating in the br'esence of the migrated sulphur from the tire carcass 'at thevulcamzing temperature causes marke d deter1oration of the rubber and in conseqence only a. relatively smal1 number of ca.sings cah be cur'ed over a. given air bag;

Also, rubber is subject to deterioftionfronr 015 the air bag, very greatly weakening the rubber and seriously and rapidly reducing the strength a.nd durability.

Similarly, when tlres are vulca.nlzed otherwise than in open steam, as in closed steam-heated molds for such purposes as retreading, or in ovens of various types th air bag is subjected to oxidizing conditions both inside and outside, and the deterioration is even more rapid.

Such a.ir bags cf the prior art are usually produced by an extrusion process and they do not ordinarily contain fabric. Instead, they are made very much thicker than ma.ny 013 the ordiuary inner tubes, to the extent of one half inch up to an inch of thickness. They am customarily made of a. mixture of rubber with a clay 1111er in about equal parts, -together with smaller qua ntities of various other ingredients. The combina-' tion of very thick walls and clay fl11er retards the curlng efl5ect of diffusing sulphur and per-' mits cf a number 01 vlcanizations an a. given tlre ?ag before lt is overcured to th point where lt The present inventlon provldes a new und userubber tire over an air bag tormed from an interpolymer of mixed olefinic and dioleflnic substences. Another object is to extend the life of the tire eir bags. Another object is to maintain the softness and flexibility of tire air bags through e prolongerl useful life. Other objects and de teils of the invention will be epparent from the following description when read in connection with the eccompenyinz drewing wherein Flg. 1 is a view in perspective of a tire eir bes eccording to the lnvention;

Fig. 2 is a view in perspective 01 an alternative form 015 e tire alr bes eccording to the invention;

Fig. 3 is e cross sectlon of the structure o the eir bag 01 the invention; and

Flg. 4 ls a view in cross sectlon of an alternative form 01 the structure of the air bez ot the invention.

The Operation 01 cracking petroleum t o increase the yiel of gasoline boiling renge hydrocerbons from crude petroleum yields also epproximetely on the crude 011 throughput 015 fixed geses consisting of hydrogen, methane and its gaseous homologues, ethylene and its gaseous homologues, etc. including e substantial percentege of isobutylene and butadiene. It is found that if isobutylene and a conjugated diolefln such es butadiene, isoprene, pentadiene-L3, or 2,3-dimethylbutadiene, are mixed in the ratio of from ebout 70 to 99 parts of isobutylene to to parts of diolefin, the specific ratio depending upon the diolefin used, and the mixture preferably dilutecl with a diluent-refrigerant such es ethylene, or propene and solid carbon dioxide; it may be polymerized by the acldition thereto of a Friedel-Crafts type oatalyst, such es aluminum chloride, dissolved. in ethyl or methyl chloride. The resulting polymer may be produoed with a molecular weight ranging from 20,000 to 250,000, depending upon the tempereture of polymerization, the purity and ratio of the reactants, solvents, etc. 'I'his polymer is a substentially seturated substence, having an iodine number lying in the range of 2 to 40 (in contrast to rubber which has an iodine number of 350 to 370, in contrest to the original isobutylene which has an iodine number of 450, and to the butediene whioh hes an iocline number of 940). The resulting polymer can be cured with sulphur to develop an elestic limit and a tensile strength ranglng from ebout 1,000 to 4,500 pounds per squere inch. When cured with sulphur, the material is substentially fully seturated chemically, and lt appeers that approximately 1 to 3% of the sulphur besed upon the weight of polymer used is sufllcient for a satisfactory cure, and sufllcient for e complete chemical saturation of the polymer substance. Further quantities of sulphur above this approxiinate amount are substentlally without efiect upon the polymer, except in so far es they behave like inert flller substances. The cur- The low unsetam'tlon 01 the polymer material thus is in consplcuous contrest to the relatively hlgh unaaturetlon 01 n'eturel rubber, and the cepebility 01 the polymer 01 ebsorbing e small emount o! sulphur to produce both a. eure and,

e oomplete chemicel saturetion of the polymer substance i.s llkewlse in outstending contreet to the cherectefistics 01 neturel rubber. In the presence 01 excess quentlties of sulpliur rubber contlnues to ebsorb the sulphur chemlcally and approeches more and more neerly the condltlon 01 a resln in whieh stete lt ls hard, brittle. nonplestic and inelestic. The present polymer me-' teriel 13 non-reeotlve with excess quentities of sulphur thereby dlflfering complcuously' trom naturel rubber. and, es above pointed out, excess quentitles of sulphur Droduce llttle o1- no eflect upon the'physlcel properties 01 the polymer.

The cured polymer producecl es above indicated shows in edd1tion the Iurther very valueble property of an outstendingly high resistence to oxidetlon. A convenient test for oxldetlon resistanca 15 the Bierer-Devis bomb procedure. This test consists in heetlng a semple 01 the material in a slow ourrent 01 substentielly pure oxygen et e pressure 015 300 pounds to the squere inch end a temperatum of 70 C. for epproxlmetely 14 deys. This test epplles p0werful oxiclizing conditions to the substences in the bomb. A high grade rubber compound 01 the type commonly used for air bags will lose approximetely 015 its tensile strength in the course 01 thls treatment. The cured copolymer material of the present invention lost epproxlmately 15% 01 its tensile strength during test treetment in the bom-b, showing e very greatly superlor oxldation resistence in comperison with the oxidetion resistance of rubber.

A modifled Iorm 01 the Bierer-Davls bomb test was then applied to samples of rubber and the polymeric material of the present invention utilizing a slow current ot substentielly pure oxygen under a pressure 01 300 pounds to the squer inch and e tempereture 01 C. for 7 days. This much more severe form of test reduced the strength 015 a rubber semple to less then 5% 01 its original strength, but reduced the strength of the polymer material 01 the present inventlon by only 18% to 20% of its original strength, leaving present in the material 80% to 82% o! the original strength es against 5% of the original strength for the rubber sample.

Furthermore, the cured polymer meterials 01 the present inventi'on are very much more steble chemlcelly in the temperature range from C. to C. then 1s the cese with rubber. and there is much less breekdown of the material, much lese lose in tensile strength, much lese lose in elasticitjr, and much greeter dureblllty then is the case with rubber.

Similarly, the polymer materl&ls of the present inventlon ere much more resistent to the eflects 01 steem and hot weter. Comperatlve tests 01 semples meintained in water et e tempereture o1! 100 C. for e period 015 7 days showed that the polymer increesed in weight by ebsorption of weter by 2.9%, wherees rubber increased in weight from ebsorption 01 weter by epproxlmately 12%.

Because o! the outstandinsly greeter resist- 9.!1oe 01 the polymer materlals both to oxygen anti to steam or hol; water, they am much suerlor to the ordlna.ry tire bags produced trom rubber.

Because of these 1'acts, t1re bass produced from the polymer may be made with much thinner walls, anti may be usedfor much langer perlods of time, und may be used for the vulcanizatlon of many more rubber tire carca.sses than ls Dos-' sible with rubber tire bags, s1nce the end o1. the life o1 a, plymer tire bag occurs only because of mechanical in.iury to the tire bas. such as tearlng or cutting, or from the unavoldabha wear und abrasion in use. However, the polymer when cured with the normal amount 01 sulphur ha.s both an abrasion reslstance end a flexure resistance which are much greater than those o! rubber and are, in fact, so great that the tire bag will outwear the reasonable average chance of destructive accident, a.nd the lite o! a tlre bag is usually not t6rminated by mere wea.r in use.

In preparing the tlre bag es shown in Flg. 1, a suitable mixture or compound" is prepared. This desirably conslsts o1 the polYmerlc material 'with suitable proportions of pigment, sulphur,

sulphurization aid, etc. For this purpose the following compoundlng" formula may be used:

(Calcene is a stearic acid treated powdered cal elum carbonate).

(In th above formula, a desirable polymer or interpolymer is that produced at a temperature of approximately 98 C. from a mixture of 80 parts isobutylene, 20 parts butadiene, 300 parts of liquid ethylene, and to 7 parts of a catalyst solution sprayed upon the surface of the mixed olefi ns. The catalyst solution desirably contains approximately 1% of aluminum chloride and is preferably cooled to a1; least 78 C. before lt is sprayed upon the mixed oleflns.)

This mix 1 prepared in two steps, the flrst consisting of mixing the polymer, zinc ox-ide, stearic acid, and sulphur in a Banbury mixer or a similar internal mixer an a temperature of approximately 140 C. for about 10 minutes. This mix is then removed end placedupon an ordinary rubber mill which is cooled to a temperature of about 70 C. or lower, and the mix millea with the rem ainder of the compounding ingredients until it becomes a smooth continuous sheet.

The compound" is then formed into the de- Sired tubular shape 3 es shown in the figures, preferably by an extruding Operation through appropriate dies. Alternatively, it may be sheeted out on the mill, slit into strips, und the strips wound on a mandrel to give the desired form, size and thickness of tube for forming the a.ir bag. The formed tubes are then cut '00 le!1gth und the ends joined as in Fig. 1, or closed over as in Fig. 2, according to the preferred type of usage.

When the structure is properly shaped, lt is desirably cured by heating in a smooth metal mold, to a temperature ranging between about 150 C. and 200 C. for a. time ranging from minutes t.o 3 hours. The mold is then opened, the a.ir bag removed, the air va1ve 4 inserted and the a.ir bag is ready for use.

The tlre casix1g as prepared ready for vulcanlzlng is then assembled with the air bag, as above described, lnslde 01 the casing end the whole inserted wlthln the mold. Th air bag ls then inflated to the deslred pressure, usually trom 20 to 150 pounds of air pressure, end the mold ls heated to the vulcanlzatlou temperature of approxlmately C. to C. for the deslred tlme, wh1ch may range from 15 mlnutes to 3 hours. A1: the close of the vulcanization, the mold ls opened und the tire removed und thereatter the a1'r bag is strippea from the inslde of the casing.

A tire air bag as so prepared ls unexpectedly efllclent for the curlng 01 rubber tlre carcasses. This appears to be due to the fact that the polymerlc a.ir bag material, belng cured wlth sumclent sulphur to saturate lt chemically, 15 lnert toward the migratory sulphur from the tlre carcass to the air bag, since the sulphur used in the original curing has fully saturated the polymer chemlcally. However, this phenomenon may be caused by other unknown factors and we do not wlsh to ofier any exact explanation of its cause.

Furthermore, 'most of the substances (except the thiuram and thiocarbonate substances) which acta as accelerators for the vulcanization of rubher are without appreciable effect upon th polymeric material and accordingly, any accelerator which may migrate from the tlre carcass to the polymerlc air bag along with the sulphur ls likewise without efiect, both because no more sulphur will combine with the polymeric materlal from the action of any accelerator end also because most of the accelerators are without effect upon the polymeric materials either alone' or in the bresence of sulphur.

Also, the sulphur in the original mlxing formula is sufllcient to saturate the polymeric material chemically, a.nd any additional sulphur which may migrate or diffuse to the alr bag from the tire carcass has little more efiect than an inert filler pigment such as clay or zinc oxlde upon the polymeric material air bag, und accordingly there is little tendency for the alr bag to over-cure and become hard and brittle.

Because of these facts, the alr bag of this invention may be milde much thinner than ls possible with a. rubber alr bag, and a. polymeric material air bag only slightly thicker than an ordinary inner tube is sufiiciently resistant to the influences of vulcanization to permit of the use of many more vulcanizations than is pdssible with a.ny torm cf rubber air bag. Thi facilitates the removal of the air bag from the vulcanized tlre.

Because of this reslstance to sulphur, lt is possible to control the extent o! yulcanizatlon o! the inner surfa.ce of the tire casing by applying a. thin layer of powdered sulphur to the inner surface of the casing to increase the sulphur coutent 015 the inner surface 015 the tlre carcass by migration cf the sulfur into it, or to reduce the sulphur content o! the inner surface by applying a thin layer of rubber containing a very low sulphur content.

Because of the high resistance of the polymer to the chemical influences of the vulcanizatlon operation, the prlncipal cause of wear upon the tire bag may in many instanc'zes be purely mechanical efiects. A still strenger a.nd more dumble air bag may be produced by the incorporation into the air bag oI a limited number 015 la.yers of fabric I as shown in Fig. 4, although this is not usually necessary. Nevertheless, the permissible thlnnes of the polymer layer to hold the air permita of the lncorporation of fabric either in the form of square woven canvas type material or in the form of cords as used for tlre carcass.

The above suggiasted mlxing formula lndicates as a preferred pigment, the substance known as Calckane." This material is not, however, an essential substance, since lt may be replaced by other fillers such as clays, various inorganic pigment substances such as ferric oxide, magnesium oxlde, barytes, and many other lnert inorganic pigments. Similarly, various organlc fillers may be used in smal1 proportion, including such substances as wood flour, ground cork, celluloslc materials generally, and similar substances.

Among the useful pigments for the mixing for-- mula is carbon black in its various types. This filler is ordinarily used only where surface abrasion is to be encountered, and is therefore not usually necessary in a tire bag. Nevertheless, in instances where tire bags are subjected to severe service, lt may be of value to incorporate into the mixture substantlal amounts of carbon black.

The air bag of the present invention is particularly advantageous for the curing of rubber tires because of its high resistance to migrating sulphur from the tire carcass. It ls however, equally usable in the preparation of other types of tires from the various synthetic rubbers, whether sulphur is a constituent of the synthetic rubber or not, since if sulphur is a canstltuent, the tire bag of the present invention has the same advantage as with rubber; and in the case of those synthetic rubbers where sulphur is not used the high strength and high abrasion resistance of the polymer tire bag of the present invention makes it particularly valuable because of the long life under severe coudltions of use and conditions which involve excessive wear upon the tire bag.

By the device cf the invention there is thus provided a new type of air bag of greatly increased durability and utility, formed from a new and useful polymeric substance, and capable of use for the curing of a greatly increased number of tire casings.

While there are above disclosed bui; a llmlted number of the embodimencs of this invention, lt is possible to produce still other embodiments without departing from the inventive concepts herein disclosed, and it is therefore desired that only such limitations be imposed on the appended claims as are stated therein or required by the prior art.

The invention claimed is:

1. In a tire vulcanization system, including a metal tire mold, means for heating the tire mold and a source of gas under pressure for expanding a tire in said tire mold; an air bag connected to sald source of gas, positioned within said tlre said air bag comprising a hollow, annular structure formed from an olefinic polymer of an isoolefln and a diolefin, the said polymer be'mg characterized by reactivity with sulphur to an extent suflicient to saturate the polymer chemically while leaving it in a strong, elastic coudltion, by inertness to larger amounts of sulphur, by a molecular weight within the range cf 20,000 to 250,000, by an iodine number within the range of from 2 to 40, and by a hlgh chemical resist ance to steam, to sulphur and to vulcanization accelerators.

2. In a tire vulcanization system, includlng a metal tire mold, means for heating the tire mold and a source of gas linder pressure for expanding a tire in said tire mold; an air-bag connected to said source of gas, positioned within said tire, said air bag comprising a hollow, annular atmeture formed from an olefinic polymer of isobutylene and butadiene, the said polymer being characterized by reactlvlty with sulphur to an extent sufllcieni to saturatr the polymer chemically while leaving lt in a strong elastic condition, by an lnertness to larger amounts o! sulphur, by a molecular weight within the range o1 20,000 to 250,000, by an iodine number wlthin the range of from 2 to 40, and by a high chemical resistance to steam, to sufphur and to vulcanizatlon accelerators.

3. In a tire curing system including a steel mold, means for heating the mold, and a source of air under pressure for expanding a tire in the mold. an alr bag connected to said compressed alr source, posltloned within said tlre, seid air bag comprislng an interpolymer of isobutylene and a diolefin, characteri2ecl by reacizlvlty with approximately 3 parts of sulphur per 100 parts of polymer, and a non-react'ivity with additional amounts of sulphur; a molecular weight withln the range of 20,000 to 250,000, an iodine number wlthln the range of 2 to 40, elasticity, a high tensile strength and high abrasion resistance;

4. In a tlre curlng system including a steel mold, means for heating the mold, and a source of air under pressure for expanding the tire in the mold, an air bag connected to sald compressed air source, positioned wlthin said tire, sald alr bag comprising an intrpolymer of isobutylene and a diolefln, characterized by reactivlty wlth approximately 3 parts of sulphur per 100 parts of polymer, and a non-reactivlty with additional amounts of sulphur; a molecular welght wlthin the tanze of 20,000 to 250,000, an iodine number within the range o1 2 to 40, elasticity, a high tensile strength and high abrasion reslstance, the said polymer substance being com-.

pounded with 3 parts of sulphur per 100 pariss of polymer.

5. In a tire curing system including a steel mold, means for heating the mold, and a source 01 air under pressure for expanding the tlre in the mold, an air bag couneoted to sald compressed alr source, positioned withln said tire, said air bag comprlsing an interpolymer of isobutylene and a dlolefln, characterized -by reactivity with approximately 3 parts of sulphur per 100 parts of polymer, and a non-reactivity with additional amounts of sulphur; a molecular welght withln the range of 20,000 to 250,000, an lodine number within the range of 2 to 40, elasticity, a high tensile strength and high abraslon reslstance, the said polymer substance being compounded with 3 parts of sulphur per 100 parts of polymer and a sulphurlzation ald.

6. In a tire curing system including a steel mold, means for heating the mold, and a source of air under pressure for expanding the tire in the mold, an air bag connected to said compressed air source, positioned within said tire, said air bag comprising an interpolymer of isobutylene and a diolefln, characterized by reactivlty with approximately 3 parts of sulphur per ;parts of polymer, and a non-reactivity with additional amounts of sulphur; a. molecular weight within the range of 20,000 to 250,000, an iodine number withln the range of 2 to 40, elasticity, a high tensile strength and hlgh abrasion resistance. the sald polymer substance beim;

compounded wlth 3 parts cf sulphur per 100 parts of polymer, a sulphurlzatlon a.id zinc oxide und stea.ric acld.

7. In a tlre curing system lncludlng a steel mold, means for heatlng the mold, and a source of air under pressure for expandlng the tlre in the mold, an alr bag connected to seid eompressed alr source, posltioned withln sald tire, seid air bag comprlslng an lnterpolymer of isobutylene und a dlolefln, characterlzed by rea.ctivity wlth approximately 3 pax1zs of sulphur per 100 par ts of polymer, and a non-reactivity with additional amounts 01 sulphur; a molecular welght wlthln the range of 20,000 to 250,000, an lodlne number wlthln the tanze of 2 to 40, elastlcity, a. high tenslle strength and hlgh abraslon resistance, the said polymer substance belng oompounded with 3 parts o! sulphur per 100 parts cf polymer, a sulphurlzation ald, zlnc oxlde, stearlc acld and carbon black.

8. A method of curlng a, large number of rubber tires comprising in comblnation the steps of lnserting the soft tire carcasses successively in a. steel mold wlth a synthetlc polymer air bag wlthin the' carcass in successlon, the a.lr ba.g belng characterized by reslstance to mlgrating sulphu.r and migra.ting vulcanizatlon accelerators whereby the chemical constitutlon and physlcal characterlstlcs of the 9.11" bag 'remaln substantially unchanged through the entlre life of the alr bag and produce no dlfierent eflfect upon the flrst carcass than upon the last carcass.

PER K. FROLICH. HARRIS D. HINELINE. 

